Substrate Redox Non-innocence Inducing Stepwise Oxidative Addition Reaction: Nitrosoarene C-N Bond Cleavage on Low-Coordinate Cobalt(0) Species
Substrate Redox Non-innocence Inducing Stepwise Oxidative Addition Reaction: Nitrosoarene C-N Bond Cleavage on Low-Coordinate Cobalt(0) Species
复制标题
底物氧化还原非无辜诱导逐步氧化加成反应：低配位钴 (0) 物种上的亚硝基芳烃 C-N 键断裂
DOI：
10.1021/jacs.9b03726
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发表时间：
2019
影响因子：
15
通讯作者：
Deng Liang
中科院分区：
文献类型：
--
作者：
Wang Dongyang;Leng Xuebing;Ye Shengfa;Deng Liang
亚硝基芳烃与过渡金属的反应对有机合成中有机氮化合物的金属催化转化以及生物学中硝基芳烃和苯胺的代谢具有重要意义。除了众所周知的金属介导的N-O键激活和亚硝基芳烃裂解的反应性外，我们在本文中首次观察到三坐标钴(0)物种[(IPr)Co(vtms)2]与2,4,6-三（叔丁基）-1-亚硝基苯（Ar*NO）相互作用时亚硝基芳烃C-N键氧化加成反应。该反应生成一个亚硝基钴基配合物[(IPr)Co(Ar*)(NO)](1)和一个二亚硝基芳烃钴配合物[(IPr)Co(η - 2- onar)(κ1-O-ONAr)](2)作为中间体。光谱表征、DFT计算和动力学研究表明，亚硝基芳烃的氧化还原非无性诱导了C-N键氧化加成反应的阶梯途径。
The reactions of nitrosoarenes with transition-metal species are fundamentally important for their relevance to metal-catalyzed transformations of organo-nitrogen compounds in organic synthesis and also the metabolization of nitroarenes and anilines in biology. In addition to the well-known reactivity of metal-mediated N–O bond activation and cleavage of nitrosoarenes, we present herein the first observation of a nitrosoarene C–N bond oxidative addition reaction upon the interaction of a three-coordinate cobalt(0) species [(IPr)Co(vtms)2] with 2,4,6-tri(tert-butyl)-1-nitroso-benzene (Ar*NO). The reaction produces a cobalt nitrosyl aryl complex, [(IPr)Co(Ar*)(NO)] (1), with a bis(nitrosoarene)cobalt complex, [(IPr)Co(η2-ONAr)(κ1-O-ONAr)] (2), as an intermediate. Spectroscopic characterizations, DFT calculations, and kinetic studies revealed that the redox non-innocence of nitrosoarene induces a stepwise pathway for the C–N bond oxidative addition reaction.